CN1685252B - Process for preparing retarders - Google Patents
Process for preparing retarders Download PDFInfo
- Publication number
- CN1685252B CN1685252B CN038229897A CN03822989A CN1685252B CN 1685252 B CN1685252 B CN 1685252B CN 038229897 A CN038229897 A CN 038229897A CN 03822989 A CN03822989 A CN 03822989A CN 1685252 B CN1685252 B CN 1685252B
- Authority
- CN
- China
- Prior art keywords
- optical anisotropic
- layer
- anisotropic layer
- liquid
- crystal compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
- Laminated Bodies (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
A novel process for preparing a rolled-up retarder comprising a transparent substrate and two or more optically-anisotropic layers respectively formed of a composition comprising a liquid-crystalline compound on or above one surface thereof. The process comprises steps for preparing plural optically anisotropic layers while keeping a long substrate unrolled and a step of rolling up the long substrate after forming all of optically-anisotropic layers thereon.
Description
Technical field
The present invention relates to a kind of preparation method with delayer of two or more optical anisotropic layers that form by the composition that comprises liquid-crystal compounds respectively.The invention still further relates to a kind of delayer, specifically, relate to a kind of record adapter of reflection LCD, CD or delayer of the quarter-wave plate in the antireflective film of can be used as by this method preparation.
Background technology
Delayer, particularly quarter-wave (λ/4) sheet can be used for various purposes and actual the use.Having described in JPA 1998-68816 and 1998-90521 (term used herein " JPA " is meant " not examining disclosed Japanese patent application ") can be by having the quarter-wave plate that λ/4 postpone overlapping the preparation at wide wavelength zone with two optical anisotropy thin polymer films.Also having described in JPA 2000-206331,2001-4837,2001-21720 and 2001-91741 can be by preparing the quarter-wave plate that has λ/4 delays at wide wavelength zone with at least two optical anisotropic layer laminations that formed by liquid-crystal compounds respectively.
In last method, must cut this two thin polymer films and must the gained small pieces are bonded to each other so that adjust the optical direction (optical axis and slow axis) of two thin polymer films and obtain required optical property at a predetermined angle.This method is too complicated, does not cause product quality to be tending towards reducing because of these axles line up, and productive rate is tending towards reducing, and production cost is tending towards increasing, because of pollution is easy to take place damage of product.And there is defective inherently in thin polymer film when accurately adjusting λ/4 slice required length of delay.
On the other hand, in one method of back, advantageously be easy to provide wide band lambda/4 slice, need an oriented layer prepare the optical anisotropic layer that the liquid crystal molecule by orientation forms.Must prepare oriented layer makes production cost increase.Also knownly comprise two during when preparation respectively by the quarter-wave plate of the optical anisotropic layer that forms of liquid crystal molecule of orientation, on the surface of more following optical anisotropic layer, do not form under the situation of oriented layer optical anisotropic layer above the preparation and often cause the degree of accuracy of liquid crystal aligning and homogeneity to reduce and produce the orientation defective, so that when the optical anisotropic layer that each liquid crystal molecule that forms by orientation forms, must form an oriented layer.
Summary of the invention
An object of the present invention is to provide a kind of can solution to the problems described above, more particularly, provide a kind of like this method, can prepare by it and to comprise two or morely respectively by the delayer of the optical anisotropic layer that forms of liquid crystal molecule of orientation, it can promote to improve the degree of accuracy and the homogeneity of liquid crystal aligning and reduce and is orientated defective and production cost.
On the one hand, the invention provides a kind of preparation method of rolling delayer, this rolling delayer comprises transparent substrate and on the one surface or the two or more optical anisotropic layers that formed by the composition that comprises liquid-crystal compounds respectively above it; This method is included in along the vertical continuous charging of long transparent substrate simultaneously in this step with formation oriented layer on the surface of long transparent substrate longitudinally, also comprises step:
(a) rub this oriented layer the surface or on this oriented layer or form above it the layer the surface;
(b) on this friction surface, apply the composition that comprises liquid-crystal compounds;
(c) composition that is coated in the step (b) on the friction surface is solidified, form an optical anisotropic layer thus;
(d) when keeping substrate to launch, step (a)-(c) is repeated at least once; With
(e) transparent substrate that has at least two optical anisotropic layers on it is rolled;
Wherein, carrying out step (d) before, do not forming oriented layer on the optical anisotropic layer that in step (c), has just formed, and more following optical anisotropic layer plays the oriented layer of the more top optical anisotropic layer of formation it on, and
The described more following optical anisotropic layer that plays on it oriented layer of the more top optical anisotropic layer that forms comprises to have and contains 9 or the still less modified polyvinylalcohol of the alkyl of carbon atom and the combination of liquid-crystal compounds.
Wherein used liquid-crystal compounds is the shaft-like liquid-crystal compounds with polymerizable groups at least one step (b); Wherein used liquid-crystal compounds is the dish type liquid-crystal compounds with polymerizable groups at least one step (b).
On the other hand, the invention provides a kind of delayer by top method preparation.
In this manual, the used term " basically " of angle is meant that this angle is in the scope that accurately angle ± 5 are spent.Preferably, spend less than ± 4, be more preferably less than ± 3 degree with the difference of this accurate angle.In this manual, term " evenly orientation " not only is used for accurate evenly orientation, and is used for the arbitrary orientation of average slope angle in the scope of 0-40 degree.In this manual, term " vertical orientated " not only is used for vertical orientated accurately, and is used for the arbitrary orientation of average slope angle in the scope of 50-90 degree.In this manual, " slow axis " is meant the direction that shows largest refractive index.
Description of drawings
Fig. 1 is the synoptic diagram that shows preparation method's process flow diagram of wave plate of the present invention.
Fig. 2 is the synoptic diagram of an example wave plate of the present invention.
Fig. 3 is to use the synoptic diagram of an example circuit polarizer sheet of wave plate of the present invention.
Fig. 4 is a floor map that shows an example process for stamping of the conventional polarizer sheet of preparation.
Fig. 5 is a floor map that shows the example process for stamping for preparing 45 ° of used polarizer sheets of the present invention.
Fig. 6 is the synoptic diagram that shows an exemplary layer structure of circuit polarizer sheet of the present invention.
Fig. 7 is the synoptic diagram that shows another exemplary layer structure of circuit polarizer sheet of the present invention.
Fig. 8 is the cross sectional planes synoptic diagram that shows the circuit polarizer sheet of embodiment 2 preparations.
Embodiment
Fig. 1 has shown an example preparation method of delayer of the present invention.Fig. 1 has shown that preparation has an exemplary method of two optical anisotropic layers.
At first, long transparent substrate (part be shown in Fig. 1) is by continuous feed, and the coating fluid that is used to form oriented layer that will comprise modified polyvinylalcohol etc. is coated on the surface of transparent substrate 1, forms oriented layer 2 (step (1)) thus.Next, use the surface (step (a)) of friction roller 3 or analog friction orientation layer 2.The coating fluid that will comprise liquid-crystal compounds is coated to cambium layer 4 on this friction surface ' (step (b)).Surface property and frictional direction according to oriented layer 2 are orientated layer 4 ' interior liquid crystal molecule with the predetermined orientation state.Then under the irradiation of heat and/or effective rays, with a kind of like this state of orientation layer 4 ' interior liquid crystal molecule is fixed, formed optical anisotropic layer 4 (step (c)) thus by polymerization etc.Repeating step (a)-(c) forms optical anisotropic layer 5 thus.Therefore can prepare the delayer that comprises two optical anisotropic layers continuously.After forming optical anisotropic layer 5, this substrate that has two optical anisotropic layers on it is rolled, and can be preserved, transport and cut into different shape and process intended application.
Although Fig. 1 has shown the preparation method of the example delay device with two optical anisotropic layers, but also step (a)-(c) can be repeated n time (wherein, n represents 2 or bigger integer, and the use of this paper back is also identical), preparation has the delayer of n layer optical anisotropic layer thus.By making delayer keep launching, promptly do not carry out step (e), up to forming all optical anisotropic layers, the present invention can prepare a kind of a plurality of optical anisotropic layers that formed by pinpoint accuracy orientation and homogeneity orientation and the few liquid crystal molecule of orientation defective respectively that comprise, though between the adjacent optical anisotropic band (Fig. 1 layers 4 and layers 5 between) do not form oriented layer.Therefore can save the step that between optical anisotropic layer, forms oriented layer like this, and help reducing production costs.
In the present invention, condition and the material that carries out step (a)-(c) for first to the n time can independent mode be selected.For example, the direction that in a plurality of steps (a), rubs or the type of used liquid-crystal compounds each other can be identical or different in a plurality of steps (b).
Next, describe used each step and different elements and the material of the present invention in detail.
[transparent substrate]
One transparent substrate is used for the present invention.It is 80% or bigger substrate that this transparent substrate in this article refers to transmittance.The wavelength dispersibility of transparent substrate is preferably little, and more particularly the ratio of preferred Re400/Re700 is less than 1.2.Transparent substrate also preferably has little optical anisotropy, and postponing (Re) in the more particularly preferred face is 20nm or littler, more preferably 10nm or littler.
Transparent substrate preferably is made up of thin polymer film.The examples of polymer that can obtain comprises cellulose esters, polycarbonate, polysulfones, polyethersulfone, polyacrylate and polymethacrylate.Wherein, preferred cellulose ester, more preferably acetylcellulose, most preferably triacetyl cellulose.Specifically with regard to the situation of using triacetyl cellulose, this compound preferably has the degree of acetylation of 60.25-61.50.This thin polymer film preferably forms by the solvent cast method.
In the present invention, use substrate with longitudinal axis.This substrate can be for rolling shape.The coating fluid that forms optical anisotropic layer is coated on the surface of this long substrate continuously.
Preferably on substrate, this substrate can be cut into the sheet of required size after all optical anisotropic layers of formation.The preferred 20-500 micron of the thickness of transparent substrate, more preferably 40-200 micron.For the cohesive between the layer that improves transparent substrate and form on it (bonding coat, even oriented layer, vertical orientated layer or optical anisotropic layer), can also (for example carry out surface treatment to transparent substrate, glow discharge processing, Corona discharge Treatment, ultraviolet ray (UV) processing, flame treatment, saponification), bonding coat (internal coating) perhaps is provided on this transparent substrate.Described surface treatment is preferably saponification.
[oriented layer]
In the present invention, when longitudinally transporting long substrate continuously, on this substrate, form oriented layer.This oriented layer has and will be coated to the function of this lip-deep liquid crystal molecule with the predetermined direction orientation.Can with by friction by organic compound (being desirably polymkeric substance) forms layer the oriented layer for preparing of surface be used for the present invention.The type that constitutes the polymkeric substance of this oriented layer decides according to the required orientation (specifically, average slope angle) of liquid crystal molecule.
For even aligned liquid-crystal molecule, the oriented layer that must use the polymkeric substance by the surface energy that does not reduce oriented layer to form.This class oriented layer is generally adopted.The example that is preferred for the polymkeric substance of this oriented layer comprises polyvinyl alcohol (PVA), polyimide derivant and nylon.
In order to improve the fusible purpose with the liquid crystal compound layer that forms thereon, the oriented layer choosing has polymerizable groups.Polymerizable groups can repetitive side chain form or add with the substituent form of cyclic group.Preferably use the oriented layer that can form chemical bond at the interface, and this oriented layer is disclosed in JPA 1997-152509 with liquid-crystal compounds.
The preferred 0.01-5 micron of the thickness of oriented layer, more preferably 0.05-3 micron.
[friction treatment]
In step (a), with the oriented layer friction that forms on the transparent substrate.Can the surface of the optical anisotropic layer of formation in the step (a)-(c) be rubbed.
Can carry out friction treatment several times along the mantle friction that constant direction will this layer with paper or cloth.The orientation of liquid crystal molecule can be determined by frictional direction.Can carry out friction treatment along direction with respect to vertical one-tenth predetermined angular of long substrate.This friction is preferred along with the direction of parallel longitudinal or along becoming the direction of the angle in-45 ° to+45 ° the scope to carry out with respect to vertical.
Although can rub by the method that is selected from various known rubbing methods, preferably use at least one friction roller.For example, with friction roller install make its with long substrate on or the surface of the layer that forms of its top contact, and when longitudinally transporting long substrate, rotate the surface of this layer so that the direction that the edge is determined by the sense of rotation of friction roller rubs.The evaluation method selecting optimal equipment that is used for this friction is equipped with the moving direction that can freely adjust friction roller and the device of the angle between the flat board.Friction roller as herein described is meant the roller that suitable friction cloth is arranged from the teeth outwards.
Next, the composition that will comprise liquid-crystal compounds is coated to this friction surface (step (b)), and said composition curing is formed optical anisotropic layer (step (c)) thus.
[optical anisotropic layer that comprises liquid-crystal compounds]
The preferably shaft-like liquid-crystal compounds of liquid-crystal compounds or the dish type liquid-crystal compounds that are used for step (b) more preferably have the shaft-like liquid-crystal compounds of polymerizable groups or have the dish type liquid-crystal compounds of polymerizable groups.
The example of shaft-like liquid-crystal compounds comprises the phenyl pyrimidine class of azomethine class, azoxy class, cyanobiphenyl class, cyanobenzene ester class, benzoates, cyclohexanecarboxylic acid phenyl ester class, cyano-phenyl cyclohexanes, cyano group replacement, phenyl pyrimidine class, Ben Ji dioxane, diphenyl acetylene class and the alkenyl cyclohexyl benzonitrile class that alkoxy replaces.Not only can use aforesaid combinations of low molecular weight liquid crystals compound, and can use the high molecular liquid-crystal compounds.Use the shaft-like liquid-crystal compounds of formula (I) representative ideally.
Formula (I)
Q
1-L
1-A
1-L
3-M-L
4-A
2-L
2-Q
2
In formula (I), Q
1And Q
2Represent polymerizable groups respectively; L
1, L
2, L
3And L
4Represent singly-bound or divalent linker respectively, prerequisite is L
3And L
4In at least one representative-O-CO-O-; A
1And A
2C2-20 is basic at interval respectively; M represents mesomorphic (mesogen) group.
The polymerisable shaft-like liquid-crystal compounds of detailed description formula (I) representative.
In formula (I), Q
1And Q
2Represent polymerizable groups respectively.This polymerizable groups can addition polymerization (but ring-opening polymerization) or can polycondensation.Preferably, Q
1And Q
2Representative can addition polymerization or the group of polycondensation respectively.The example that has shown polymerizable groups below.
-SH -OH -NH
2
L
1, L
2, L
3And L
4Respectively Dai Biao divalent linker preferably be selected from one of following group :-O-,-S-,-CO-,-NR
2-,-CO-O-,-O-CO-O-,-CO-NR
2-,-NR
2-CO-,-O-CO-,-O-CO-NR
2-,-NR
2-CO-O-,-NR
2-CO-NR
2-and singly-bound.R
2Represent C1-7 alkyl or hydrogen atom.L
3And L
4In at least one representative-O-CO-O-(carbonate group).
At Q
1And L
1Combination or Q
2And L
2The group of combination representative in, preferred embodiment comprises CH
2=CH-CO-O-, CH
2=C (CH
3)-CO-O-and CH
2=C (Cl)-CO-O-, preferred example is CH
3=CH-CO-O-.
A
1And A
2Represent C2-20 base at interval respectively, preferred C2-12 aliphatic group, more preferably alkylidene.The interval base is the chain base preferably, and can contain oxygen atom not adjacent to each other or sulphur atom.Base can have substituting group at interval, and especially can be replaced by halogen atom (fluorine, chlorine, bromine), cyano group, methyl or ethyl.
The mesogen group of M representative can be selected from known mesogen group arbitrarily.Its preferred embodiment is represented by following formula (II).
Formula (II)
-(-W
1-L
5)
n-W
2-
In formula (II), W
1And W
2Represent divalence alicyclic group, divalent aryl or divalent heterocycle respectively.L
5Be singly-bound or linking group.L
5The example of the linking group of representative comprises L in the above-mentioned formula (I)
1-L
4Shown in the instantiation of representative those ,-CH
2-O-and-O-CH
2-." n " is 1,2 or 3 integer.
W
1And W
2Example comprise cyclohexane-1,4-two bases, 1,4-phenylene, pyrimidine-2,5-two bases, pyridine-2,5-two bases, 1,3,4-thiadiazoles-2,5-two bases, 1,3,4-Evil thiadiazoles-2,5-two bases, naphthalene-2,6-two bases, naphthalene-1,5-two bases, thiophene-2,5-two base and pyridazines-3,6-two bases.1,4-cyclohexane two bases can be trans-and cis-steric isomer exist, wherein above-mentioned any one and all can be used for the present invention with any mixture of any mixing ratio.More preferably trans forms.W
1And W
2Can have substituting group independently; and substituent instantiation (for example comprises halogen atom (fluorine, chlorine, bromine, iodine), cyano group, C1-10 alkyl; methyl, ethyl, propyl group), the C1-10 alkoxy (for example; methoxyl, ethoxy), the C1-10 acyl group (for example; formoxyl, acetyl group), the C1-10 alkoxy carbonyl (for example; methoxycarbonyl, ethoxy carbonyl), C1-10 acyloxy (for example, acetoxyl group, propionyloxy), nitro, trifluoromethyl and difluoromethyl.
The preferred embodiment that shows the mesogen group of above-mentioned formula (II) representative below, however the mesogen group is not limited to these examples.The Mesogen group can be replaced by any substituting group recited above.
The instantiation of the compound that display type (I) is represented is understood that wherein the present invention never is limited to this below.Can be by the compound of the representative of the method preparation formula (I) described in the JPA 1999-513019.
Various dish type liquid-crystal compoundss can be used for the present invention as liquid-crystal compounds.Dish type liquid-crystal compounds relative thin face is vertical orientated ideally, and promptly the pitch angle is in the scope of 50-90 degree.The example of dish type liquid-crystal compounds comprises the benzene derivative described in " the 111st page (1981) of Mol.Cryst. the 71st volume, C.Destrade etc. "; Alkane (truxane) derivant is avenged in telling described in " the 141st page (1985) of Mol.Cryst. the 122nd volume, C.Destrade etc. " and " Physics Lett.A. the 78th rolls up the 82nd page (1990) "; Cyclohexane derivant described in " the 70th page (1984) of Angew.Chem. the 96th volume, B.Kohn etc. "; And aza-crown or the phenylacetylene described in " the 1794th page of J.Chem.Commun. (1985), M.Lehn etc. " and " the 2655th page (1994) of J.Am.Chem.Soc. the 116th volume, J.Zhang etc. " based on little ring (microcycls).
The liquid-crystal compounds that is used to prepare optical anisotropic layer does not need to keep liquid crystal liquid crystal property after in being included in optical anisotropic layer.For example,, cause the polymerization or the cross-linking reaction of this compound by light and/or heat, and carry out this reaction, form this layer thus when having when the combinations of low molecular weight liquid crystals compound of light and/or the hot reactive group that causes is used to prepare optical anisotropic layer.Can no longer present liquid crystal liquid crystal property through polymerization or crosslinked compound.The polyreaction of dish type liquid-crystal compounds is described among the JP-A 1996-27284.
The dish type liquid crystal molecule has polymerizable groups ideally with by its polymerization is fixed.Yet, when directly polymerizable groups being linked to each other with the dish type core, during polyreaction, be tending towards being difficult to keeping orientation.Therefore, the dish type liquid-crystal compounds is included in the linking group between dish type core and the polymerizable groups ideally.That is, the dish type liquid-crystal compounds is represented by following formula (III) ideally.
Formula (II)
D(-L-P)
n
In the formula, D represents the dish type core, and L represents divalent linker, and P represents polymerizable groups, and n represents the integer of 4-12.The preferred embodiment of dish type core " D ", divalent linker " L " and polymerizable groups " P " is identical with example (P1)-(P18) with the example (D1)-(D15) described in the JPA 2001-4837, example (L1)-(L25) respectively.
In these optical anisotropic layers, these liquid crystal molecules with basically uniformly mode be orientated, more preferably with basically evenly the mode of orientation fix, most preferably fix by polyreaction.With regard to the situation of shaft-like liquid-crystal compounds that use has polymerizable groups, preferably evenly in the orientation shaft-like molecule is fixed basically keeping." even basically " as herein described is meant that the average slope angle between the face of the long axis direction of shaft-like molecule and optical anisotropic layer falls in the scope of 0-40 degree.Can also perhaps make the pitch angle gradually change, i.e. hybrid orientation shaft-like liquid crystal molecules tilt orientation through orientation.Even under tilted alignment or hybrid orientation, this average slope angle also preferably falls in the scope of 0-40 degree.
With regard to the situation of dish type liquid-crystal compounds that use has polymerizable groups, preferably when keeping the perpendicular orientation, compound is fixed." perpendicular " as herein described is meant at the average slope angle between the face of disc-shaped surface and optical anisotropic layer in the scope of 50-90 degree.Can also perhaps make the pitch angle gradually change, i.e. hybrid orientation dish type liquid crystal molecules tilt orientation through orientation.Even under the situation of tilted alignment or hybrid orientation, this average slope angle is also preferred in the scope of 50-90 degree.
In the present invention, step (a)-(c) is repeated the layer that n time (n be 2 or bigger integer) forms optical anisotropic layer thus, wherein preferably can play a part passing through the oriented layer of the optical anisotropic layer of step (a)-(c) formation for the n time to (n-1) inferior each optical anisotropic layer that forms by step (a)-(c) for the first time.With regard to the situation that more following optical anisotropic layer can play the oriented layer effect of the more top optical anisotropic layer of formation on it, preferably in step (b), use to have and contain 9 or the still less modified polyvinylalcohol of the alkyl of carbon atom and the combination of liquid-crystal compounds, in step (c), form optical anisotropic layer thus, and the surface of the optical anisotropic layer that friction forms thus in follow-up step (a).
Next, detailed description can be mixed having of using with liquid-crystal compounds and be contained 9 or the modified polyvinylalcohol of the alkyl of carbon atom still less.
The modified polyvinylalcohol of preferred formula (PX) representative.
Formula (PX)
-(VAl)
x-(HyD)
y-(VAc)
z-
In formula (PX), " VAl " is based on the repetitive of vinyl alcohol, and " HyD " has to contain 9 or the repetitive of the alkyl of carbon atom still less, and " VAc " is based on the repetitive of vinyl acetate; X is 20-95 weight %, is 25-95 weight % ideally; Y is 2-98 weight %, is 10-80 weight % ideally; Z is 0-30 weight %, is 2-20 weight % ideally.Term " alkyl " is used for any aliphatic group, any aryl and combination in any thereof.Aliphatic group can have ring-type or straight or branched structure.Aliphatic group is alkyl (comprising naphthenic base) or alkenyl (comprising cycloalkenyl group) ideally.Alkyl can have at least one substituting group.The carbon number that comprises in the alkyl is 1-9, is 1-8 ideally.
" HyD " is to have to contain 9 or the repetitive of the alkyl of carbon atom still less, preferably by formula (HyD-I) or (HyD-II) expression.
In these formulas, L
1Be be selected from following divalent linker :-O-,-CO-,-SO
2-,-NH-, alkylidene, arlydene and combination in any thereof; L
2Be singly-bound or be selected from following divalent linker :-O-,-CO-,-SO
2-,-NH-, alkylidene, arlydene and combination in any thereof; And R
1And R
2Representative contains 9 or the alkyl of carbon atom still less respectively.The instantiation that shows the linking group that forms by combinations thereof below.
L
1：-O-CO-
L
2:-O-CO-alkylidene-O-
L
3:-O-CO-alkylidene-CO-NH-
L
4:-O-CO-alkylidene-NH-SO
2-arlydene-O-
L
5:-arlydene-NH-CO-
L6:-arlydene-CO-O-
L7:-arlydene-CO-NH-
L8:-arlydene-O-
L9:-O-CO-NH-arlydene-NH-CO-
The instantiation that shows " HyD " below.
Be used for polymkeric substance of the present invention as adjuvant and preferably have 200-5, the degree of polymerization and 9 of 000 (more preferably 300-3,000), 000-200, the molecular weight of 000 (more preferably 13,000-130,000).Two or more polymer mixed can be used.
The instantiation that shows polymkeric substance below, yet, can be used for polymkeric substance of the present invention and be not limited to these examples.
PX-1：-(VAl)
21-(HyD-13)
77-(VAc)
2-
PX-2：-(VAl)
14-(HyD-13)
84-(VAc)
2-
PX-3：-(VAl)
21-(HyD-16)
77-(VAc)
2-
PX-4：-(VAl)
34-(HyD-15)
64-(VAc)
2-
PX-5：-(VAl)
29-(HyD-12)
69-(VAc)
2-
PX-6：-(VAl)
46-(HyD-14)
52-(VAc)
2-
PX-7：-(VAl)
21-(HyD-2)
77-(VAc)
2-
PX-8：-(VAl)
17-(H)D-8)
85-(VAc)
2-
PX-9：-(VAl)
21-(HyD-13)
7-(VAc)
2-
PX-10：-(VAl)
46-(HyD-9)
52-(VAc)
2-
With respect to the weight of liquid-crystal compounds, in the optical anisotropic layer amount of modified polyvinylalcohol ideally in the scope of 0.05-10 weight %, preferred 0.1-5 weight %.
Modified polyvinylalcohol can mix use with at least a condensation agent.Condensation agent is the compound that has isocyanates or formoxyl endways ideally.The instantiation that shows condensation agent below, yet, can be used for condensation agent of the present invention and be not limited to these examples.
Poly-(1, the 4-butylene glycol), end is an isophorone diisocyanate
Poly-(1, the 4-butylene glycol), end is a methylene phenyl 2, the 4-diisocyanate
Poly-(hexane diacid second diester), end is a methylene phenyl 2, the 4-diisocyanate
Poly-(propylene glycol), end is a methylene phenyl 2, the 4-diisocyanate
1,6-diisocyanate hexane
1, the 8-diisocyanate octane
1,12-diisocyanate dodecane
Isophorone diisocyanate
Glyoxal
In step (b), preferably will for example comprise liquid-crystal compounds, and if necessary, dissolving wherein aforementioned modified polyvinylalcohol, polymerization initiator or the composition of the coating fluid of other adjuvant of listing below be coated to friction surface.Preferably with an organic solvent prepare coating fluid.The example of organic solvent comprises that amide-type (for example, N, dinethylformamide), sulfoxide class (for example, dimethyl sulfoxide), heterogeneous ring compound (for example, pyridine), hydrocarbon are (for example, benzene, hexane), the alkyl halide class (for example, chloroform, methylene chloride), ester class (for example, methyl acetate, butyl acetate), ketone (for example, acetone, methyl ethyl ketone) and ethers (for example, tetrahydrofuran, 1, the 2-dimethoxy-ethane).Wherein, preferred alkyl halogen class and ketone.Two or more organic solvents can also be mixed.Can carry out the coating (for example, extrusion coated method, direct intaglio plate rubbing method, reverse intaglio plate rubbing method and mould are coated with method) of coating fluid by the method for any known.
[fixing of the state of orientation of liquid crystal molecule]
In step (c), the above-mentioned coating fluid that is coated on the friction surface is solidify to form optical anisotropic layer.Liquid crystal molecule can be by the performance of oriented layer and the state of orientation orientation of frictional direction decision.Preferably when keeping this state of orientation fixedly liquid crystal molecule form optical anisotropic layer thus.Preferably implementing by the polyreaction that joins the polymerizable groups in the liquid-crystal compounds should be fixing.Polyreaction comprises the heat polymerization that uses polymerization initiator so that the photopolymerization reaction that can carry out polyreaction and use Photoepolymerizationinitiater initiater under being heated is so that can carry out polyreaction under dynamic rays, the wherein preferred latter.The example of Photoepolymerizationinitiater initiater comprises that the alpha-carbonyl compound (is described in United States Patent (USP) 2367661,2367670), acyloin ethers (being described in United States Patent (USP) 2448828), the fragrant acyloin compound (being described in United States Patent (USP) 27,225 12) that α-hydrocarbon replaces, multinuclear naphtoquinone compounds (being described in United States Patent (USP) 3046127 and 2951758), the combination of triarylimidazoles dipolymer and p-aminophenyl ketone (being described in United States Patent (USP) 3549367), acridine or compound phenazine (are described in the interim publication number 60-105667 of Jap.P., United States Patent (USP) 4239850) are with oxadiazole compound (being described in United States Patent (USP) 4212970).
Based on the solid in the coating fluid, the consumption of Photoepolymerizationinitiater initiater is 0.01-20% weight preferably, is more preferably 0.5-5% weight.The ray that the polymerisable liquid crystal molecule is used preferably uses ultraviolet ray.The preferred 20mJ/cm of irradiation energy
2-50mJ/cm
2, more preferably 100mJ/cm
2-800mJ/cm
2Can in heating, shine, to quicken photopolymerization reaction.
The ideal thickness ground of optical anisotropic layer is the 0.1-10 micron, more preferably the 0.5-5 micron.
[optical property of delayer]
The optical anisotropic layer that preferably forms in above-mentioned steps guarantees that differing under specific wavelength roughly is p or p/2.Differing p and can be adjusted to λ/2 by the length of delay of the optical anisotropic layer will specific wavelength (λ) measured down and obtain under specific wavelength (λ), and differ p/2 and can be adjusted to λ/4 acquisitions by the length of delay of the optical anisotropic layer will specific wavelength (λ) measured down.When delayer comprises two optical anisotropic layers, preferably produce and differ p at the two-layer down one deck of 550nm (roughly falling into the middle wavelength of visible region), another layer generation differs p/2.At two optical anisotropic layers is by step (a)-(c) being repeated under twice the sample situation, the length of delay that an optical anisotropic layer (first optical anisotropic layer) is measured under 550nm is 240-290nm preferably, be more preferably 250-280nm, the length of delay that another optical anisotropic layer (second optical anisotropic layer) is measured under 550nm is 110-145nm preferably, is more preferably 120-140nm.
The length of delay of this paper is meant on optical anisotropic layer length of delay in the face of the light definition of normal direction incident, and is specifically provided by following equation:
Length of delay (Re)=(nx-ny) xd
Wherein, nx and ny represent the interior principal refractive index of the face of optical anisotropic layer, and d represents the thickness (nm) of optical anisotropic layer.
The thickness of optical anisotropic layer can arbitrary decision, as long as this layer can present required length of delay.Comprise at delayer under the sample situation of two optical anisotropic layers, two-layerly all form by the identical shaft-like liquid-crystal compounds of even orientation, one of them generation differs p, another generation differs p/2, and the thickness that produces the optical anisotropic layer that differs p preferably produces the twice of the thickness of the optical anisotropic layer that differs p/2.Difference is generally the 0.1-10 micron, preferred 0.2-8 micron, more preferably 0.5-5 micron although the preferable range of the thickness of single optical anisotropic layer can be according to the type of used liquid-crystal compounds.
[structure of delayer]
Fig. 2 is the synoptic diagram that shows the representative construction of delayer of the present invention, and it comprises two optical anisotropic layers that formed by the composition that comprises shaft-like liquid-crystal compounds.As shown in Figure 2, basic delayer comprises long transparent substrate (S), first optical anisotropic layer (A) and second optical anisotropic layer (B).First optical anisotropic layer (A) produces and differs p, and second optical anisotropic layer (B) produces and differs p/2.The slow axis (a) of vertical and first optical anisotropic layer (A) of transparent substrate (S) is with 30 ° of intersections.The slow axis (b) of second optical anisotropic layer (B) and the slow axis (a) of first optical anisotropic layer (A) are with 60 ° of intersections of angle (γ).First optical anisotropic layer (A) shown in Figure 1 and second optical anisotropic layer (B) contain shaft-like liquid crystal molecule (c1 and c2) respectively.Shaft-like liquid crystal molecule c1 and c2 evenly are orientated.The longitudinal axis of shaft-like liquid crystal molecule (c1 and c2) is corresponding to the slow axis (a and b) of optical anisotropic layer.
Although for convenience's sake, Fig. 2 has shown a kind of like this example constructions of delayer, wherein (it is nearer to differ=p) be installed in distance transparent substrate (S) for optical anisotropic layer (A), and optical anisotropic layer (B) (differs=p/2) is installed in the outside, but also can change optical anisotropic layer (A) and position (B).Yet, a kind of preferred structure be for example with optical anisotropic layer (A) (differ=p) mounting distance transparent substrate (S) is nearer, optical anisotropic layer (B) (differ=p/2) than the outside.
[circuit polarizer sheet]
Delayer of the present invention is useful when on the quarter-wave plate that the record adapter or the antireflective film that are used at reflection LCD, CD use.This quarter-wave plate usually and linearly polarizing film constitute the circuit polarizer sheet.Therefore the quarter-wave plate that constitutes the circuit polarizer sheet with linearly polarizing film easily can be joined in the equipment such as reflection LCD.The example of linearly polarizing film comprises and contains the iodine linearly polarizing film, uses containing the dyestuff linearly polarizing film and containing the polyene linearly polarizing film of dichroic dye.Usually use film preparation to contain the iodine linearly polarizing film and contain the dyestuff linearly polarizing film based on poly-(vinyl alcohol).
[structure of circuit polarizer]
Fig. 3 is the synoptic diagram that shows the representative construction of the circuit polarizer sheet of the present invention that comprises delayer shown in Fig. 2, and this delayer comprises two optical anisotropic layers that formed by the composition that comprises shaft-like liquid-crystal compounds.Circuit polarizer sheet shown in Fig. 3 comprises the transparent substrate shown in Fig. 2 (S), first optical anisotropic layer (A) and second optical anisotropic layer (B), also comprises linearly polarizing film (P).Vertical (s) of the polarization transmission axis (p) of linearly polarizing film (P) and transparent substrate (S) is with 45 ° of intersections, the slow axis (a) of this polarization transmission axis (p) and first optical anisotropic layer (A) is with 15 ° of intersections, and with similar shown in Fig. 2, the slow axis (a) of first optical anisotropic layer (A) and the slow axis (b) of second optical anisotropic layer (B) are with 60 ° of intersections.First optical anisotropic layer (A) and second optical anisotropic layer (B) shown in same Fig. 3 contain shaft-like liquid crystal molecule (c1 and c2) respectively.Shaft-like liquid crystal molecule (c1 and c2) is orientation evenly.The longitudinal axis of shaft-like liquid crystal molecule (c1 and c2) is corresponding to slow axis (a and b) in the face of optical anisotropic layer (A and B).
Have no particular limits with the linearly polarizing film of delayer of the present invention combination, wherein the example that can obtain comprises and contains the iodine linearly polarizing film, uses containing the dyestuff linearly polarizing film and containing the polyene linearly polarizing film of dichroic dye.Contain the iodine linearly polarizing film and contain the dyestuff linearly polarizing film and form by film usually based on poly-(vinyl alcohol).Linearly polarizing film preferably so superposes with delayer of the present invention, so that the orientation obliquely vertical at 45 of the transparent substrate of its axis of homology and delayer.The linearly polarizing film (this paper back abbreviates " 45 ° of linearly polarizing films " as) that use has with the polarization transmission axis of vertical inclination at 45 makes its angle that no longer needs to adjust stack, and is convenient to prepare circuit polarizer sheet of the present invention.Owing to the axis of homology of the linearly polarizing film that is formed by oriented film is consistent with draw direction basically, therefore the direction oriented film with vertical inclination at 45 with it can successfully make 45 ° of linearly polarizing films.These 45 ° of linearly polarizing films can make by the direction oriented film in vertical inclination at 45 of film relatively, and structure of described condition, available devices or the like is described in [0009]-[0045] section among the JPA 2002-86554.
The thin polymer film that stretches among the present invention is had no particular limits, therefore can utilize to comprise arbitrarily the suitably film of thermoplastic polymer.The example of this polymkeric substance comprises polyvinyl alcohol (PVA) (PVA), polycarbonate, cellulose acylate and polysulfones.The preferred PVA that uses is as this polymkeric substance.Although PVA normally obtains by the saponification polyvinyl acetate, PVA also can contain any component that can close with vinyl acetate copolymerization, for example unsaturated carboxylic acid, unsaturated sulfonic acid, alkene and vinyl ethers.Can also use the modified PVA that contains acetoacetyl, sulfonic group, carboxyl, oxo alkylidene etc.
Although the saponification degree to PVA has no particular limits, consider from the angle of solubleness etc., preferably be adjusted in the scope of 80-100mol%, more preferably 90-100mol%.Although the degree of polymerization to PVA also has no particular limits, preferably be adjusted to 1,000-10, in 000 the scope, more preferably 1,500-5,000.
Dyeing can produce linearly polarizing film to PVA, and wherein colouring method can be undertaken by adsorbing from vapor phase or liquid phase.In the exemplary method of the liquid phase adsorption of using iodine,, the PVA film absorbs by being immersed in the IKI aqueous solution.The amount of iodine and potassium iodide preferably is respectively 0.1-20g/L and 1-100g/L, and the weight ratio of iodine and potassium iodide is preferably in the scope of 1-100.Dyeing time is 30-5 preferably, and in 000 second, solution temperature is preferably in 5-50 ℃ scope.This colouring method is not limited only to soak, and can adopt any-mode for example be coated with or spray iodine or dye solution.This colouring method can be prior to drawing process or after drawing process.And because the suitable swelling of film and therefore be convenient to stretch wherein, so that the dyeing before stretching is coated with is useful.
Except iodine, it also is preferred using dichroic dye dyeing.The instantiation of dichroic dye comprises following dye composition: azo dyes, stilbene dye, butazolidin dyestuff, kiton colors, quinoline dye, oxazine dye, thiazin dyes and anthraquinone dye.Although preferred water-soluble these, be not limited to this.Also preferred these dichroic dyes wherein add hydrophilic substituent, for example sulfonic group, amino and hydroxyl.The instantiation of dichroic dye comprises that C.I. is directly yellow 12, C.I. direct orange 39, C.I. direct orange 72, C.I. are directly red 39, C.I. is directly red 79, C.I. is directly red 81, C.I. is directly red 83, C.I. is directly red 89, C.I. is directly purple 48, C.I. is directly blue 67, C.I. is directly blue 90, C.I. direct green 59, C.I. acid red 37, and is described among JPA 1989-161202,1989-172906,1989-172907,1989-183602,1989-248105,1989-265205 and the 1995-261024 those.These dichroic molecules are used with the form of free acid, alkali metal salt, ammonium salt or amine salt.Two or more these dichroic molecules mixing are successfully made the polarizer with various colors.The compound (dyestuff) or the potpourri that design the different dichroic molecules that present black in being contained in polarizer element or polarizer sheet and when its axis of homology is orthogonal are preferred, and this is because they have high transmittance and high polarization ratio with monolithic form.
When stretching PVA prepares linearly polarizing film, preferably add adjuvant and PVA is crosslinked.Particularly under the situation that adopts inclination drawing process of the present invention, because the tension force in this method may make the direction of orientation of PVA not overlap, unless this PVA film enough solidifies in the outlet of drawing process, therefore preferred before drawing process or during make by the solution that soaks or be coated with this crosslinking chemical and to contain this crosslinking chemical in the PVA film.Disclosed crosslinking chemical in U.S.'s reissue patent 232897 can be used for the present invention, wherein most preferably use the boric acid class.
This drawing process also is used to prepare so-called polyvinyl linearly polarizing film ideally, and polarization function wherein is attributable to by dehydration and dechlorination PVA and gathers conjugated double bond in the polyene structure that (vinyl chloride) obtain.
45 ° of linearly polarizing films are by vertically making with the direction oriented film of 45 ° of inclinations with respect to film; can still more preferably on its one or both sides, be used as the polarizer sheet after the lamination protective film without any being configured to the polarizer sheet under changing and being used as delayer of the present invention.Kind to protective film has no particular limits, and its utilizable example comprises cellulose esters such as cellulose acetate ester, cellulose acetate-butyrate ester and cellulose propionate ester; Polycarbonate; Polyolefin; Polystyrene; And polyester.Yet it is not desirable that the length of delay of protective film surpasses certain value, and this is owing to do not overlap in the axis of homology of protective film and the inclination between the axis of orientation and can cause linear polarization to be converted into circular polarization.The length of delay of protective film is preferably little, its normally 10nm or littler, more preferably 5nm or littler under 632.8nm.Preferred especially cellulose triacetate has the polymkeric substance of the protective film of this low-level length of delay as formation.Use polyolefin for example ZEONEX and ZEONOR (trade name, the product of Japanese ZEON company) and ARTON (trade name, the product of Japanese JSR company) ideally.Other utilizable example comprises the non-birefringence optics resin material described in JPA 1996-110402 and the 1999-293116.
Although operable bonding agent has no particular limits between linearly polarizing film and protective seam; but can utilize PVA resin (comprising PVA) and boron compound aqueous solution with modifications such as acetoacetyl, sulfonic group, carboxyl, oxyalkylenes; wherein, preferred PVA resin.The thickness of bonding agent drying layer preferably in the scope of 0.01-10 micron, more preferably 0.05-5 micron.
Although the film thickness before stretching is had no particular limits, considers the homogeneity of film clamping stability and stretching, the preferred 1 micron-1mm of film thickness, more preferably 20-200 micron.
Figure 4 and 5 have shown the example punching press pattern of traditional polarizer sheet and the example punching press pattern of polarizer sheet of the present invention respectively.Traditional polaroid as shown in Figure 4, has absorption axes 71, and promptly tensile axis is consistent with vertical 72.On the other hand, polarizer sheet of the present invention, as shown in Figure 5, absorption axes 81 with polarization, it is tensile axis, with vertical 82 inclinations at 45, wherein this pitch angle and polarizer sheet (through and the liquid crystal cell of LCD bonding) absorption axes and the angle between liquid crystal cell itself vertical or horizontal consistent, and make it in punching course, no longer need to tilt punching press like this.Be clear that from Fig. 5 this polarizer sheet can make by rip cutting longitudinally, rather than, also be useful therefore that this is because the line of cut of preparation polarizer sheet of the present invention longitudinally extends as the crow flies, and guarantees the productive rate excellence like this by the punching press preparation.
Consider the contrast that improves LCD, be used for polarizer sheet of the present invention and preferably have high transmittance and high degree of polarization.Transmittance preferred 30% or bigger under 550nm, more preferably 40% or bigger.Degree of polarization preferred 95.0% or bigger under 550nm, more preferably 99% or bigger, even more preferably 99.9% or bigger.
Linearly polarizing film all has protective film usually on two surface.In the present invention, delayer of the present invention can play the protective film of a side of linear polarization film.Just use 45 ° of linearly polarizing films to prepare with regard to the situation of circuit polarizer sheet, by changing stack manner can easily prepare right hand formula and left-hand type in mode optionally circuit polarizer sheet.
[structure of circuit polarizer sheet]
Fig. 6 has shown the synoptic diagram of an embodiment of circuit polarizer sheet of the present invention.
Circuit polarizer sheet shown in Figure 6 through configuration in case on delayer of the present invention stacked 45 ° of linearly polarizing film P and protective film G.This delayer comprises optical anisotropic layer A and B (showing with individual layer among the figure) and transparent substrate.With the so stacked so that transparent substrate of this delayer and 45 ° of linearly polarizing film P with its on be formed with the surperficial facing surfaces of optical anisotropic layer A and B and the surface of 45 ° of linearly polarizing film P is installed contiguously.In this structure, delayer also plays the protective film of 45 ° of linearly polarizing film P.Fig. 6 also be presented at transparent substrate S vertically, the mutual relationship between the axis of homology p of slow axis a, the b of optical anisotropic layer A, B and 45 ° of linearly polarizing film P.
When joining circuit polarizer sheet shown in Figure 6 in the display, the protective film of P side points to display surface side (the arrow indication view direction among the figure).The circular polarization that obtains by the structure shown in Fig. 6 is right hand formula polarized light.Light is gone out then by linearly polarizing film P and optical anisotropic layer A, B, and as right hand formula polarized light from the direction shown in the arrow among Fig. 6.
Another example constructions that has shown circuit polarizer sheet of the present invention among Fig. 7.Circuit polarizer sheet shown in Fig. 7 has following structure: with the exchange of the position of protective film G shown in the prior figures 6 and delayer, wherein protective film G, 45 ° of linearly polarizing film P, transparent substrate S and optical anisotropic layer A, B are upwards stacked successively.Therefore the circuit polarizer sheet of structure can produce the left-hand type polarized light.
As above apparent, when protective film G and delayer are adhered to 45 ° of linearly polarizing film P, only just can optionally obtain right hand formula polarized light and left-hand type polarized light by changing stacked top and bottom.
With regard to regard to the situation of also using protective film the transparent substrate, protective film preferably constitutes by having high optically isotropic cellulose ester film, wherein preferred especially triacetylcellulose film.
λ/4 of the wide region that the delayer of the application of the invention and polarizer sheet obtain refer in particular at all ratios of length of delay/wavelength of measuring under 450nm, 550nm and the 650nm all in the scope at 0.2-0.3.The ratio of length of delay/wavelength preferably in the scope of 0.21-0.29, more preferably 0.22-0.28, even more preferably 0.23-0.27, most preferably 0.24-0.26.
Embodiment
Below with reference to specific embodiment the present invention is described in more detail.Can suitably improve any materials, reagent, usage ratio and operation not deviating under the spirit of the present invention.Therefore should understand scope of the present invention never is limited to the following examples.
[embodiment 1]
Use thick 80 microns, wide 680mm and long 500m, degree of acetylation be 60.9 ± 0.2% and length of delay be that the optical isotropy triacetylcellulose film of 6.0nm is as transparent substrate.With two surperficial saponification of this transparent substrate, and on one surface, apply coating fluid " A " continuously, use NH
4OH is adjusted to 4-5 with the pH of this coating fluid, in order to the preparation oriented layer, and the thick 1 micron layer of dry formation.This layer also with respect to the angle of 30 ° of vertical one-tenth of transparent substrate through continuous friction treatment.Prepare oriented layer thus.
The composition of coating fluid " A ":
Below shown in modification poly-(vinyl alcohol): 4 weight %
Water 72.6 weight %
Methyl alcohol 23.3 weight %
Glutaraldehyde 0.2 weight %
Using rod to be coated with device will be coated on the surface of oriented layer continuously with the following coating fluid that consists of the basis preparation, drying, and heating (orientation slaking) with the ultraviolet ray irradiation, forms optical anisotropic layer (A) more thus, and thickness is 2.1 microns.Find that this optical anisotropic layer (A) has at the slow axis with respect to the direction of 30 ° of inclinations of vertical one-tenth of transparent substrate, the length of delay under the 550nm (Re550) is 259nm.
The composition of the coating fluid of optical anisotropic layer (A):
Shaft-like liquid-crystal compounds 38.1 weight %
(example compound I-2)
Below shown in photosensitizer (A) 0.38 weight %
Below shown in Photoepolymerizationinitiater initiater (B) 1.14 weight %
Example compound in this instructions (PX-9) 0.19 weight %
Glutaraldehyde 0.04 weight %
Methyl ethyl ketone 60.1 weight %
Then the direction of thus obtained optical anisotropic layer (A) in-60 ° of inclinations of its slow axis one-tenth relatively rubbed continuously with the direction that relatively vertically becomes-30 ° of inclinations, keep film to launch afterwards at preparation optical anisotropic layer (A) simultaneously.
Use rod to be coated with device and will be coated to the friction surface of optical anisotropic layer (A) continuously based on the coating fluid of following composition preparation, it is dry to keep film to launch after friction simultaneously, heating (orientation slaking), again with the ultraviolet ray irradiation, form optical anisotropic layer (B) thus, thickness is 1.0 microns.Prepare delayer (λ/4 slice) thus.The average delay value of measuring under the 550nm (Re550) is 136nm.Angle between the slow axis of the vertical and optical anisotropic layer (B) of transparent substrate is shown in table 1.
The composition of the coating fluid of optical anisotropic layer (B):
Shaft-like liquid-crystal compounds 38.4 weight %
(example compound I-2)
Above shown in photosensitizer (A) 0.38 weight %
Above shown in Photoepolymerizationinitiater initiater (B) 1.15 weight %
Below shown in orientation adjust agent (C) 0.06 weight %
Methyl ethyl ketone 60.0 weight %
[comparative example 1]
In the method for embodiment 1, on each substrate, form optical anisotropic layer (A) and afterwards this substrate is rolled once, under 25 ℃, the environment of 60%RH (relative humidity), leave standstill the listed time in the table 1 with roll-up state.Surface as 1 pair of optical anisotropic layer of embodiment (A) rubs afterwards; Form optical anisotropic layer (B) by coating then, form each delayer thus corresponding to comparative example 1-3.Angle between the slow axis of the optical anisotropic layer (B) of the vertical and single sample of transparent substrate is shown in table 1.
Table 1
From found that shown in the table 1, the angle vertically and in the face between the slow axis of optical anisotropic layer (B) that is presented at transparent substrate at the sample that optical anisotropic layer (A) leaves standstill with deployed condition afterwards has less variation, and this explanation liquid-crystal compounds evenly is orientated also maintenance ideal value.This has confirmed effect of the present invention.
With regard to following situation, form optical anisotropic layer (A) afterwards, the surface that the aforementioned coating fluid " A " that forms oriented layer is coated to layer (A) is 1 micron layer with formation thickness.As forming optical anisotropic layer (B) by aforementioned coating fluid as described in the comparative example 1-3 to the friction surface coat (B) of oriented layer.Do not observe transparent substrate as shown in table 1 vertically and the variation of the interior angle of the face between the slow axis of optical anisotropic layer (B), its result is identical with embodiment's 1.The angle variation with after the roll-up state storage shown in this obvious instruction card 1 is attributable on optical anisotropic layer (A) and does not form oriented layer, and the present invention is effective to the situation that does not form oriented layer between two optical anisotropic layers.
[embodiment 2]
The PVA film was soaked for 240 seconds down in 25 ℃ in the aqueous solution that contains 2.0g/L iodine and 4.0g/L potassium iodide, in the 10g/L boric acid aqueous solution, soaked for 60 seconds down then, join it in stenter stretcher of constructing shown in Fig. 2 of JPA 2002-86554 and stretch 5.3 times in 25 ℃.Stenter keeps its constant width afterwards from the draw direction bending shown in Figure 2 of JPA 2002-86554 then, under shrinking under 80 ℃ of environment with this film drying, take off from stenter then.Moisture with dry PVA film afterwards before mensuration stretches is respectively 31% and 1.5%.
The difference of travelling speed of measuring a left side and right stenter folder is less than 0.05%, and the center line of the film of adding and the angle delivered between next step the center line of film are 46 °.Measuring | L1-L2| and W are 0.7m, and | L1-L2|=W.Be determined at the roughly draw direction Ax-Cx and center line 22 inclinations at 45 of delivering to next step film of the outlet of stenter.Shrinkage or distortion are not observed in outlet at stenter.
Also use 3%PVA (PVA-117H, the product of Kuraray company limited) aqueous solution is as the cellulose triacetate film (FUJITACK of bonding agent with this film and saponification, the product of Fuji Photo Film Co., Ltd., length of delay=3.0nm) bonding, dry under 80 ℃, obtaining effective width thus is the polarizer sheet of 650mm.
Measure the absorption axes that gained polarizer sheet has vertical inclination at 45 with it, and transmittance and the degree of polarization of mensuration gained polarizer sheet under 550nm is 43.7% and 99.97% respectively.Film is cut into the size of 310 * 233mm, as shown in Figure 5, successfully obtain absorption axes inclination at 45 and area efficiency and be 91.5% polarizer sheet.
Next, as shown in Figure 8, be laminated on the surface that contains iodine linearly polarizing film 91 for preparing above by delayer 96 preparation among the embodiment 1, and the anti-dazzle antireflective film 97 of lamination saponification on the apparent surface, prepare another circuit polarizer sheet 92.Prepare other polarizer sheet 93-95 similarly, just use the delayer of making each among the comparative example 1-3 to replace delayer 96 respectively.In the preparation method of all these circuit polarizer sheets, lamination is vertical to guarantee each each other with linearly polarizing film and delayer.
Use up (450nm, 550nm and 650nm) from thus obtained each the circuit polarizer sheet 92-95 of anti-dazzle antireflective film 97 sides irradiation, in wide 650mm and long 1, any 20 points in the zone of 000mm are measured the (length of delay: Re), represent variation range by maximal value and minimum value that differs of transmitted light.The results are shown in table 2.
Table 2
As shown in table 2, method of the present invention successfully prepares the circuit polarizer sheet that the interior Re of face only has a small amount of variation.
[embodiment 3: the preparation of reflection LCD]
From industrial reflection LCD (" Color Zaurus MI-310 ", the product of Japanese Sharp company), take off polarizer sheet and delayer, and replace loading onto the circuit polarizer sheet 92 of preparation among the embodiment 2.
The visual evaluation of thus obtained reflection LCD confirms, all shows neutral gray in the arbitrary patterns that white demonstration, black display and shadow tone show, does not have display color.
Next, use the contrast ratio of visual angle determining instrument (EZcontrast160D, the product of French Eldim SA) mensuration based on reflecting brightness, find that the contrast ratio that face side is measured is 10, it has enough been used.
Industrial applicibility
The present invention can be used for reducing the manufacturing cost of the delayer that comprises two or more optical anisotropic layers, and described layer is formed by the liquid crystal molecule of orientation respectively, has eliminated many orientation defectives.
Claims (5)
1. the preparation method of a rolling delayer, this rolling delayer comprises transparent substrate and on the one surface or the two or more optical anisotropic layers that formed by the composition that comprises liquid-crystal compounds respectively above it; This method is included in along the vertical continuous charging of long transparent substrate simultaneously in this step with formation oriented layer on the surface of transparent substrate longitudinally, also comprises step:
(a) rub this oriented layer the surface or on this oriented layer or form above it the layer the surface;
(b) on the surface of friction, apply the composition that comprises liquid-crystal compounds at this;
(c) the lip-deep composition that is coated in the step (b) through friction is solidified, form an optical anisotropic layer thus;
(d) when keeping substrate to launch, step (a)-(c) is repeated at least once; With
(e) transparent substrate that has at least two optical anisotropic layers on it is rolled,
Wherein, carrying out step (d) before, do not forming oriented layer on the optical anisotropic layer that in step (c), has just formed, and more following optical anisotropic layer plays the oriented layer of the more top optical anisotropic layer of formation it on, and
The described more following optical anisotropic layer that plays on it oriented layer of the more top optical anisotropic layer that forms comprises to have and contains 9 or the still less modified polyvinylalcohol of the alkyl of carbon atom and the combination of liquid-crystal compounds.
2. method as claimed in claim 1, wherein said modified polyvinylalcohol is expressed from the next:
-(VAl)
x-(HyD)
y-(VAc)
z-
Wherein " VAl " is based on the repetitive of vinyl alcohol, and " HyD " has to contain 9 or the repetitive of the alkyl of carbon atom still less, and " VAc " is based on the repetitive of vinyl acetate; X is 20-95 weight %, and y is 2-98 weight %, and z is 0-30 weight %, and x, y and z sum are 100 weight %.
3. as the method for claim 1 or 2, wherein used liquid-crystal compounds is the shaft-like liquid-crystal compounds with polymerizable groups at least one step (b).
4. as the method for claim 1 or 2, wherein used liquid-crystal compounds is the dish type liquid-crystal compounds with polymerizable groups at least one step (b).
5. one kind is passed through the delayer that each described method of claim 1-4 prepares.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP280795/2002 | 2002-09-26 | ||
| JP2002280795A JP4117173B2 (en) | 2002-09-26 | 2002-09-26 | Production method of retardation plate and retardation plate produced by the method |
| PCT/JP2003/012324 WO2004029695A2 (en) | 2002-09-26 | 2003-09-26 | Processe for preparing retarders |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1685252A CN1685252A (en) | 2005-10-19 |
| CN1685252B true CN1685252B (en) | 2011-09-28 |
Family
ID=32040497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN038229897A Expired - Fee Related CN1685252B (en) | 2002-09-26 | 2003-09-26 | Process for preparing retarders |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP4117173B2 (en) |
| KR (1) | KR100970355B1 (en) |
| CN (1) | CN1685252B (en) |
| AU (1) | AU2003264944A1 (en) |
| TW (1) | TWI293373B (en) |
| WO (1) | WO2004029695A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110095828A (en) * | 2018-01-30 | 2019-08-06 | 唯亚威通讯技术有限公司 | Optical device with optical property and engineering properties |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004021248A1 (en) * | 2004-04-30 | 2005-11-24 | Giesecke & Devrient Gmbh | Security element and method for its production |
| JP4485350B2 (en) * | 2004-12-28 | 2010-06-23 | 大日本印刷株式会社 | Method for producing retardation film |
| JP2006220682A (en) * | 2005-02-08 | 2006-08-24 | Fuji Photo Film Co Ltd | Optical compensation sheet and manufacturing method for the same, polarizing plate and liquid crystal display |
| TWI384305B (en) * | 2005-06-23 | 2013-02-01 | Sumitomo Chemical Co | Method of producing otpical film |
| JPWO2009025170A1 (en) * | 2007-08-23 | 2010-11-25 | コニカミノルタオプト株式会社 | Long retardation film, long elliptically polarizing film, elliptically polarizing plate, and image display device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5853801A (en) * | 1995-09-04 | 1998-12-29 | Fuji Photo Film Co., Ltd. | Process for the preparation of continuous optical compensatory sheet |
| JP2001091741A (en) * | 1999-09-22 | 2001-04-06 | Fuji Photo Film Co Ltd | Phase difference plate and circularly polarizing plate |
| JP2002258053A (en) * | 2001-03-05 | 2002-09-11 | Dainippon Printing Co Ltd | Optical element extracting circularly polarized light, method of manufacturing the same, polarized light source device and liquid crystal display |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI243264B (en) * | 2000-12-04 | 2005-11-11 | Fuji Photo Film Co Ltd | Optical compensating sheet and process for producing it, polarizing plate and liquid crystal display device |
| TW557369B (en) * | 2000-12-20 | 2003-10-11 | Dainippon Printing Co Ltd | Circularly polarized light extraction optical element and method of manufacturing the optical element |
-
2002
- 2002-09-26 JP JP2002280795A patent/JP4117173B2/en not_active Expired - Fee Related
-
2003
- 2003-09-25 TW TW092126428A patent/TWI293373B/en not_active IP Right Cessation
- 2003-09-26 WO PCT/JP2003/012324 patent/WO2004029695A2/en active Application Filing
- 2003-09-26 KR KR1020057005113A patent/KR100970355B1/en active IP Right Grant
- 2003-09-26 AU AU2003264944A patent/AU2003264944A1/en not_active Abandoned
- 2003-09-26 CN CN038229897A patent/CN1685252B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5853801A (en) * | 1995-09-04 | 1998-12-29 | Fuji Photo Film Co., Ltd. | Process for the preparation of continuous optical compensatory sheet |
| JP2001091741A (en) * | 1999-09-22 | 2001-04-06 | Fuji Photo Film Co Ltd | Phase difference plate and circularly polarizing plate |
| JP2002258053A (en) * | 2001-03-05 | 2002-09-11 | Dainippon Printing Co Ltd | Optical element extracting circularly polarized light, method of manufacturing the same, polarized light source device and liquid crystal display |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110095828A (en) * | 2018-01-30 | 2019-08-06 | 唯亚威通讯技术有限公司 | Optical device with optical property and engineering properties |
| US11360242B2 (en) | 2018-01-30 | 2022-06-14 | Viavi Solutions Inc. | Optical device having optical and mechanical properties |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003264944A1 (en) | 2004-04-19 |
| WO2004029695A3 (en) | 2004-07-08 |
| KR100970355B1 (en) | 2010-07-15 |
| CN1685252A (en) | 2005-10-19 |
| TW200415373A (en) | 2004-08-16 |
| KR20050073460A (en) | 2005-07-13 |
| AU2003264944A8 (en) | 2004-04-19 |
| WO2004029695A2 (en) | 2004-04-08 |
| TWI293373B (en) | 2008-02-11 |
| JP2004151122A (en) | 2004-05-27 |
| JP4117173B2 (en) | 2008-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105492935B (en) | Brightness enhancement film, optics chip part and liquid crystal display device | |
| KR100679436B1 (en) | Optical compensation sheet having optical anisotropic layer formed from liquid crystal molecules | |
| CN100375910C (en) | Broad-band-cholesteric liquid-crystal film, process for producing the same, circularly polarizing plate, linearly polarizing element, illuminator, and liquid-crystal display unit | |
| JP6000916B2 (en) | Liquid crystal display device, retardation film and polarizing plate | |
| JP2001004837A (en) | Phase difference plate and circular polarization plate | |
| JP2001183643A (en) | Liquid crystal display device | |
| US20090237599A1 (en) | Optical film, polarizing plate, and liquid crystal display device | |
| JP2001021720A (en) | Phase difference plate and circular polarizing plate | |
| CN101546011B (en) | Optical film, polarizing plate, and liquid crystal display device | |
| JP2006317736A (en) | Optical film and liquid crystal display device | |
| JPWO2005040903A1 (en) | Liquid crystal display device having liquid crystal cell of bend alignment mode or hybrid alignment mode | |
| CN1685252B (en) | Process for preparing retarders | |
| JP5394662B2 (en) | Optical film, polarizing plate, and liquid crystal display device | |
| JP2000206331A (en) | Phase difference plate and elliptic polarizing plate | |
| JP2007079347A (en) | Optical film, polarizer using same, and liquid crystal display device | |
| KR20070112236A (en) | Liquid crystal cell and liquid crystal display apparatus | |
| JP4344566B2 (en) | Method for producing optical compensation film | |
| CN101685174B (en) | Laminated optical film, polarizing plate and liquid crystal display device | |
| TWI356212B (en) | Optical compensation film, liquid crystal display | |
| JP4330321B2 (en) | Retardation plate, manufacturing method thereof, and circularly polarizing plate using the same | |
| JP6487777B2 (en) | LAMINATE, WINDOW AND METHOD OF MANUFACTURING LAMINATE | |
| JP2004184964A (en) | lambda/4 PLATE | |
| JP2009086378A (en) | Optical compensation film, polarizing plate and liquid crystal display | |
| JP2004333720A (en) | Method for manufacturing rolled optical compensation film, rolled optical compensation film, polarizing plate, and liquid crystal display device | |
| JP2005157330A (en) | Optical compensation sheet and liquid crystal display |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: FUJI PHOTO FILM CO., LTD. Free format text: FORMER OWNER: FUJIFILM HOLDINGS CORP. Effective date: 20070928 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20070928 Address after: Tokyo, Japan Applicant after: FUJIFILM Corp. Address before: Tokyo, Japan Applicant before: Fujifilm Corp. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110928 Termination date: 20210926 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |